WO2019018357A1 - Catalyseur et procédés associés impliquant une hydrosilylation et une silylation déshydrogénante - Google Patents

Catalyseur et procédés associés impliquant une hydrosilylation et une silylation déshydrogénante Download PDF

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Publication number
WO2019018357A1
WO2019018357A1 PCT/US2018/042421 US2018042421W WO2019018357A1 WO 2019018357 A1 WO2019018357 A1 WO 2019018357A1 US 2018042421 W US2018042421 W US 2018042421W WO 2019018357 A1 WO2019018357 A1 WO 2019018357A1
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Prior art keywords
catalyst
compound
silicon
group
unsaturated
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PCT/US2018/042421
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English (en)
Inventor
Debashis Basu
Aswini K. Dash
Thomas B. Rauchfuss
Ryan Gilbert WATSON
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Dow Silicones Corporation
Board Of Trustees Of The University Of Illinois
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Priority to JP2019571309A priority Critical patent/JP7174724B2/ja
Priority to US16/632,150 priority patent/US10946368B2/en
Priority to CN201880044594.2A priority patent/CN110944748B/zh
Priority to EP18749709.4A priority patent/EP3655157A1/fr
Publication of WO2019018357A1 publication Critical patent/WO2019018357A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C07F7/0879—Hydrosilylation reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0896—Compounds with a Si-H linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
    • B01J2540/225—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate comprising perfluoroalkyl groups or moieties

Definitions

  • the present invention generally relates to a catalyst and, more specifically, to a catalyst for hydrosilylation and/or dehydrogenative silylation and related methods, as well as to a method of preparing the catalyst and a composition including the same.
  • Hydrosilylation reactions are generally known in the art and involve an addition reaction between silicon-bonded hydrogen and aliphatic unsaturation. Hydrosilylation reactions are utilized in various applications. For example, curable compositions may rely on hydrosilylation reactions for purposes of curing or crosslinking components of the curable compositions. Hydrosilylation reactions may also be utilized to prepare individual components or compounds, e.g. components for inclusion in curable compositions.
  • Dehydrogenative silylation reactions are also known in the art and similarly involve a reaction between silicon-bonded hydrogen and aliphatic unsaturation. However, in dehydrogenative silylation, there is no addition reaction, and instead the aliphatic unsaturation bonds to silicon. Dehydrogenative silyation reactions may be utilized to prepare unsaturated compounds (e.g. olefin functional compounds) which may further undergo a hydrosilylation reaction.
  • unsaturated compounds e.g. olefin functional compounds
  • the present invention provides a catalyst having the following structure:
  • each R is an independently selected substituted or unsubstituted hydrocarbyl group
  • [M] has formula M'X n L m , where M' is a metal selected from Fe, Co, and Ni; each X is independently a halogen atom, an alkoxy group, an amide group, an alkyl group, a silyl group, or H; each L is independently an olefin, an agostic C-H, an agostic Si-H, an ether, a nitrile, or N2; n is 0, 1 , or 2, and m is 0, 1 , or 2.
  • the present invention also provides a method of preparing the catalyst.
  • the method comprises complexing a metal compound with a ligand to give the catalyst.
  • the metal compound has the formula M'X2, wherein M' is a metal selected from Fe, Co, and Ni and each X is independently a halogen atom.
  • the ligand has the following structure:
  • each R is an independently selected substituted or unsubstituted hydrocarbyl group.
  • a method of preparing a catalytic reaction product comprises reductively activating the catalyst with an activating compound to prepare the catalytic reaction product.
  • the catalytic reaction product, and a catalyst mixture of the catalyst and the activating compound are also provided.
  • the present invention further provides a composition.
  • the composition comprises (A) an unsaturated compound including at least one aliphatically unsaturated group per molecule, subject to at least one of the following two provisos: (1 ) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • the composition further comprises (C) the catalyst.
  • a method of preparing a hydrosilylation reaction product comprises reacting an aliphatically unsaturated group and a silicon-bonded hydrogen atom in the presence of (C) a hydrosilylation catalyst to give the hydrosilylation reaction product.
  • the aliphatically unsaturated group is present in (A) an unsaturated compound; wherein at least one of the following two provisos applies: (1 ) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the silicon-bonded hydrogen atom is present in (B) a silicon hydride compound separate from the (A) unsaturated compound.
  • the (C) hydrosilylation catalyst comprises the catalyst set forth above.
  • a method of preparing a dehydrogenative silylation reaction product is provided, along with the dehydrogenative silylation reaction product formed in accordance with the method.
  • the method comprises reacting an aliphatically unsaturated group and a silicon-bonded hydrogen atom in the presence of (C") a silylation catalyst to prepare the dehydrogenative silylation reaction product.
  • the aliphatically unsaturated group is present in (A) an unsaturated compound; wherein at least one of the following two provisos applies: (1 ) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the silicon-bonded hydrogen atom is present in (B) a silicon hydride compound separate from the (A) unsaturated compound.
  • the (C") silylation catalyst comprises the catalyst set forth above.
  • the present invention provides a catalyst.
  • the catalyst has excellent physical properties and may be utilized at least in hydrosilylation reactions and/or dehydrogenative silylation reactions.
  • a method of preparing the catalyst is also disclosed, along with a composition comprising the catalyst. Given the diverse end use applications of the catalyst and its catalytic activity, a method of preparing a hydrosilylation reaction product and a method of preparing a dehydrogenative silylation reaction product with the catalyst are also disclosed.
  • the hydrosilylation react product and the dehydrogenative silylation reaction product may be utilized in diverse end use applications, as described in greater detail below.
  • the catalyst has the followi
  • each R is an independently selected substituted or unsubstituted hydrocarbyl group;
  • M has formula M'X n L m , where M' is a metal selected from Fe, Co, and Ni; each X is independently a halogen atom, an alkoxy group, an amide group, an alkyl group, a silyl group, or H; each L is independently an olefin, an agostic C-H, an agostic Si-H, an ether, a nitrile, or N2; n is 0, 1 , or 2, and m is 0, 1 , or 2.
  • Subscripts n and m generally correspond to an oxidation state of the M' metal and the particular ligands represented by X and L. X and L may bond or complex to one another.
  • the halogen atoms optionally represented by X and L are not limited and are independently selected. In certain embodiments, the halogen atoms are selected from CI and Br.
  • each X is typically a halogen atom.
  • [M] may be FeCl2, FeBr2, FeBrCI,
  • each halogen atom is the same in [M].
  • [M] has formula M'X2
  • the catalyst has the following structure:
  • Each R which is independently selected, may be linear, branched, cyclic, or combinations thereof.
  • Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups.
  • Aryl groups may be monocyclic or polycyclic.
  • Linear and branched hydrocarbyl groups may independently be saturated or unsaturated.
  • One example of a combination of a linear and cyclic hydrocarbyl group is an aralkyl group.
  • Substituted hydrocarbyl groups are hydrocarbyl groups having one or more atoms (e.g. C and/or H) replaced (i.e., substituted) with another atom or substituent (i.e., group), for example, a halogen atom such as chlorine, fluorine, bromine or iodine, an oxygen atom, an oxygen atom containing group such as an acrylic, methacrylic, alkoxy, or carboxyl group, a nitrogen atom, a nitrogen atom containing group such as an amino, amido, or cyano group, a sulphur atom, or a sulphur atom containing group such as a mercapto group.
  • a halogen atom such as chlorine, fluorine, bromine or iodine
  • an oxygen atom an oxygen atom containing group such as an acrylic, methacrylic, alkoxy, or carboxyl group
  • a nitrogen atom a nitrogen atom containing group such as an amino,
  • substituted hydrocarbyl groups include propyl groups substituted with chlorine or fluorine, such as 3,3,3-trifluoropropyl groups, chloro- and alkoxy-phenyl groups, beta-(perfluorobutyl)ethyl groups, chlorocyclohexyl groups, and heteroaryls such as pyridinyl groups.
  • Hydrocarbyl groups may be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, or similar alkyl groups; vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl, or similar alkenyl groups; phenyl, tolyl, xylyl, naphthyl, or similar aryl groups; benzyl, phenethyl, or similar aralkyl groups; and 3-chloropropyl, 2-bromoethyl, 3,3,3- trifluoropropyl, or similarly substituted (e.g.
  • each R is independently selected based on a factor such as steric hindrance, electronics (e.g. electron donative, inductive, or withdrawing effects), and the like, or combinations thereof.
  • R may be selected to impart chirality or to impart symmetry to the catalyst.
  • R may be independently selected to enforce reactive regioselectivity, such as anti-Markovnikov selectivity.
  • each R is independently non-linear, e.g. branched or cyclic (e.g. aryl).
  • R may be isopropyl, isobutyl, t-butyl, other branched alkyl.
  • R may be substituted aryl, e.g. pentafluorophenyl.
  • each R in the catalyst is the same. As but two specific examples, each R is isopropyl, or each R is pentafluorophenyl.
  • iPr means isopropyl and M' and X are defined above.
  • additional ligands represented by X or L may be present in the catalyst, and the examples above are merely exemplary examples.
  • the catalyst may be in or on a solid carrier.
  • carriers include activated carbons, silicas, silica aluminas, aluminas, zeolites and other inorganic powders/particles (e.g. sodium sulphate), and the like.
  • the catalyst may also be disposed in a vehicle, e.g. a solvent which solubilizes the catalyst, alternatively a vehicle which merely carries or disperses, but does not solubilize, the catalyst.
  • vehicle e.g. a solvent which solubilizes the catalyst
  • vehicle which merely carries or disperses, but does not solubilize
  • Such vehicles are known in the art.
  • the vehicle or solvent, or a moiety thereof may complex with the M' metal and become a ligand represented by X or L.
  • Suitable vehicles include polyorganosiloxanes, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other polyorganosiloxanes.
  • the vehicle may comprise an organic solvent.
  • the organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n- butyl ether, a halogenated hydrocarbon such as dichloromethane, 1 ,1 ,1 -trichloroethane or methylene chloride; chloroform; dimethyl s
  • [M] of the catalyst upon its formation is of formula IWX2, where each X is typically a halogen atom.
  • the M' metal may complex with the vehicle or solvent, or a moiety thereof, if present along with the catalyst.
  • X and/or L may be something other than a halogen atom.
  • the catalyst may be activated prior to and/or during any reaction catalyzed therewith.
  • a catalyst mixture is also provided.
  • the catalyst mixture comprises the catalyst and an activating compound.
  • the activating compound influences or modifies the catalytic activity of the catalyst.
  • the activating agent may influence the complex of the M' metal and ligands X and L (e.g. may decomplex ligands X and/or L, if present in the catalyst and complexed to the M' metal). This generally increases catalytic activity of the catalyst by allowing the M' metal to complex with other ligands while catalyzing a reaction.
  • the activating compound typically reductively activates the catalyst. Reductively activating the catalyst generally comprises reducing the formal oxidation state of the M' metal.
  • the activating compound is i) a borohydride compound; (ii) an aluminum hydride compound; (iii) an organolithium compound; (iv) an organomagnesium compound; or (v) any combination of (i) to (iv).
  • the borohydride compound may be, for example, a metal borohydride such as sodium triethylborohydride (NaEt3BH), lithium triethylborohydride (LiEt3BH), or sodium borohydride.
  • suitable activating compounds include an alkalimetal amalgam; hydrogen; a metal hydride such as sodium naphthalenide; a silyl hydride; etc.
  • Suitable reducing agents include those described in Chem. Rev. 1996, 96, 877-910.
  • the relative amounts of the catalyst and the activating compound may vary depending, for example, on the selection of the catalyst, including the M' metal and its oxidation state, the ligands represented by X and/or L, the number of hydrogen atoms present within the activating compound, etc.
  • the catalyst including the M' metal and its oxidation state, the ligands represented by X and/or L, the number of hydrogen atoms present within the activating compound, etc.
  • One of skill in the art readily understands how to determine proper molar ratios in view of these selections.
  • the catalyst mixture typically forms a reaction product upon the activating compound reductively activating the catalyst.
  • a catalytic reaction product formed from the catalyst mixture is also provided.
  • the catalytic mixture and/or the catalytic reaction product is typically utilized when catalyzing the reaction, which may be formed prior to or contemporaneous with catalyzing the reaction (e.g. formed in situ).
  • the catalyst mixture and/or the catalytic reaction product may be formed in situ in the presence of the components catalyzed by the catalyst mixture and/or the catalytic reaction product.
  • a method of preparing the catalytic reaction product comprises reductively activating the catalyst with the activating compound to prepare the catalytic reaction product.
  • the method comprises combining the catalyst and the activating compound, which then react via the activating compound reductively activating the catalyst.
  • reductively activating the catalyst typically occurs when the catalyst is in the presence of the activating compound without further steps of initiating.
  • the catalyst and the activating compound may be combined in any manner, with any equipment, optionally while disposed in a vehicle or with other components, and optionally under shear or mixing.
  • a method of preparing the catalyst comprises complexing a metal compound with a ligand to give the catalyst.
  • the metal compound has the formula IWX2, wherein M' and X are defined above.
  • the ligand has the followin
  • the catalyst may be prepared in a vehicle, such as any of the vehicles described above.
  • the catalyst may be prepared in the vehicle in which the catalyst is disposed during use thereof.
  • the catalyst is prepared in the presence of tetrahydrofuran.
  • the ligand may be provided, obtained, or prepared.
  • the method of preparing the catalyst further comprises preparing the ligand prior to and/or in conjunction with complexing the metal compound with the ligand.
  • the ligand can be prepared or synthesized via numerous paths or techniques.
  • the ligand can be prepared according to the reaction scheme set forth below:
  • the present invention also provides a composition.
  • the composition comprises (A) an unsaturated compound.
  • the (A) unsaturated compound includes at least one aliphatically unsaturated group per molecule, which may alternatively be referred to as ethylenic unsaturation.
  • the (A) unsaturated compound is not limited and may be any unsaturated compound having at least one aliphatically unsaturated group.
  • the (A) unsaturated compound comprises an organic compound.
  • the (A) unsaturated compound comprises a siloxane.
  • the (A) unsaturated compound comprises a silicone-organic hybrid, or an organosilicon compound.
  • Various embodiments and examples of the (A) unsaturated compound are disclosed below.
  • the (A) unsaturated compound includes an average of at least two aliphatically unsaturated groups per molecule.
  • the (A) unsaturated compound is capable of polymerization.
  • the aliphatically unsaturated groups of the (A) unsaturated compound may be terminal, pendent, or in both locations in the (A) unsaturated compound.
  • the aliphatically unsaturated group may be an alkenyl group and/or an alkynyl group.
  • Alkenyl group means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon double bonds.
  • the alkenyl group may have from 2 to 30 carbon atoms, alternatively from 2 to 24 carbon atoms, alternatively from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 10 carbon atoms, alternatively from 2 to 6 carbon atoms.
  • Alkenyl groups are exemplified by, but not limited to, vinyl, allyl, propenyl, and hexenyl.
  • Alkynyl group means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon- carbon triple bonds.
  • the alkynyl group may have from 2 to 30 carbon atoms, alternatively from 2 to 24 carbon atoms, alternatively from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 10 carbon atoms, alternatively from 2 to 6 carbon atoms.
  • Alkynyl is exemplified by, but not limited to, ethynyl, propynyl, and butynyl.
  • the (A) unsaturated compound has the formula R 1 — Z'—
  • Z' is a divalent linking group, which may be a divalent hydrocarbon, a polyoxyalkylene, a polyalkylene, a polyisoalkylene, a hydrocarbon-silicone copolymer, a siloxane, or mixtures thereof.
  • Z' may be linear or branched. In these specific embodiments,
  • R 1 is independently selected and includes aliphatic unsaturation, i.e., R 1 is independently selected from alkenyl groups and alkynyl groups.
  • the (A) unsaturated compound includes two aliphatically unsaturated groups represented by R 1 .
  • Z' is a divalent hydrocarbon.
  • the divalent hydrocarbon Z' may contain 1 to 30 carbons, either as aliphatic or aromatic structures, and may be branched or unbranched.
  • the linking group Z' may be an alkylene group containing 1 to 12 carbons.
  • the (A) unsaturated compound may be selected from a, ⁇ -unsaturated hydrocarbons.
  • the a, ⁇ -unsaturated hydrocarbons may alternatively be referred to as olefins.
  • the (A) unsaturated compound may be any diene, diyne or ene-yne compound.
  • the (A) unsaturated compound may be referred to as an ⁇ , ⁇ -unsaturated hydrocarbon.
  • Suitable diene, diyne or ene-yne compounds include 1 ,4- pentadiene, 1 ,5-hexadiene; 1 ,6-heptadiene; 1 ,7-octadiene, 1 ,8-nonadiene, 1 ,9-decadiene, 1 ,1 1 -dodecadiene, 1 ,13-tetradecadiene, and 1 ,19-eicosadiene, 1 ,3-butadiyne, 1 ,5- hexadiyne (dipropargyl), and 1 -hexene-5-yne.
  • the (A) unsaturated compound may alternatively have the formula R-Z", where is defined above and Z" is a monovalent hydrocarbon group.
  • the (A) unsaturated compound includes one aliphatically unsaturated group represented by R 1 .
  • Ethylene includes only one aliphatically unsaturated group, and does not include any divalent or monovalent linking group. Ethylene may be utilized in gaseous form as the (A) unsaturated compound.
  • the composition is typically formed in a vessel, which may optionally be pressured, with ethylene.
  • the vessel may be pressured with ethylene at a pressure that is greater than atmospheric pressure, which can further drive the reaction. Temperatures may be elevated in the vessel as well.
  • the (A) unsaturated compound may be referred to as an unsaturated hydrocarbon, and may be any -ene or -yne compound.
  • the (A) unsaturated compound may be an acyclic alkene and/or an acyclic alkyne.
  • the (A) unsaturated compound may include aryl groups so long as the (A) unsaturated compound also includes the at least one aliphatically unsaturated group independent from any aryl groups.
  • the (A) unsaturated compound comprises, alternatively is, a polyether.
  • the (A) unsaturated compound comprises a polyoxyalkylene group having the formula (C a H 2a O), wherein a is from 2 to 4 inclusive. With reference to the general formula above, 71 is the polyoxyalkylene group.
  • the (A) unsaturated compound may be referred to as the polyoxyalkylene.
  • the polyoxyalkylene may comprise oxyethylene units (C2H4O), oxypropylene units
  • the (A) unsaturated compound as the polyoxyalkylene may have the following general formula:
  • each R1 is independently selected and defined above, c is from 0 to 200, d is from 0 to 200, and e is from 0 to 200, with the proviso that c, d and e are not simultaneously 0.
  • c is from 0 to 50, alternatively from 0 to 10, alternatively from 0 to 2.
  • d is from 0 to 100, alternatively 1 to 100, alternatively 5 to 50.
  • e is from 0 to 100, alternatively 0 to 50, alternatively 0 to 30.
  • the ratio of (d+e)/(c+d+e) is greater than 0.5, alternatively greater than 0.8, or alternatively greater than 0.95.
  • the polyoxyalkylene set forth above is merely one exemplary example of a suitable polyoxyalkylene.
  • the polyoxyalkylene group comprises only oxypropylene units (C3H6O).
  • H 2 C C(CH 3 )CH 2 [C 3 H 6 0] d
  • CH 2 C(CH 3 ) CH 2
  • polyoxybutylene or poly(oxytetramethylene) containing polyoxyalkylenes include:
  • polyoxyalkylenes suitable for (A) the unsaturated compound include two aliphatically unsaturated groups.
  • the polyoxyalkylene suitable for (A) the unsaturated compound may include only one aliphatically unsaturated group.
  • the polyoxyalkylene suitable for (A) the unsaturated compound may alternatively have the following general formula:
  • R 1 , c, d, and e are defined above, and R 2 is H or an alkyl group, such as CH3. Any description or examples above also apply to this embodiment as well.
  • R 1 , c, d, and e are defined above, and R 2 is H or an alkyl group, such as CH3. Any description or examples above also apply to this embodiment as well.
  • One of skill in the art readily understands how the examples of polyoxyalkylenes above with two aliphatically unsaturated groups may alternatively include but one aliphatically unsaturated group.
  • the polyoxyalkylene may be prepared by, for example, the polymerization of ethylene oxide, propylene oxide, butylene oxide, 1 ,2-epoxyhexane, 1 ,2-epoxyoctance, and/or cyclic epoxides, such as cyclohexene oxide or exo-2,3-epoxynorborane.
  • the polyoxyalkylene moiety of the polyoxyalkylene may comprise oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene units (C4H3O), or mixtures thereof.
  • the polyoxyalkylene group comprises a majority of oxypropylene or oxybutylene units, as defined on a molar basis and indicated in the above formula by the c, d, and e subscripts.
  • R 1 -Z" of the (A) unsaturated compound comprises a polyalkylene group.
  • the polyalkylene group may comprise from C2 to CQ alkylene units or their isomers.
  • One specific example is polyisobutylene group, which is a polymer including isobutylene units.
  • the (A) unsaturated compound may be a di-allyl terminated polyisobutylene or an allyl-terminated polyisobutylene.
  • the molecular weight of the polyisobutylene group may vary, but typically ranges from 100 to 10,000 g/mole.
  • the (A) unsaturated compound comprises an organopolysiloxane.
  • the organopolysiloxane is not limited and may be any organopolysiloxane including at least one silicon-bonded aliphatically unsaturated group per molecule.
  • the organopolysiloxane may be linear, branched, partly branched, cyclic, resinous (i.e., have a three-dimensional network), or may comprise a combination of different structures.
  • the aliphatically unsaturated group is silicon-bonded (e.g. as silicon- bonded alkenyl and/or silicon-bonded alkynyl).
  • the organopolysiloxane has the following average formula: R 5 fSiO (4 _f)/2
  • each is an independently selected substituted or unsubstituted hydrocarbyl group with the proviso that in each molecule, at least one, alternatively at least two, groups is an aliphatically unsaturated group, and wherein f is selected such that 0 ⁇ f ⁇ 3.2.
  • the average formula above for the organopolysiloxane may be alternatively written as (R ⁇ 3SiO-
  • /2) W (R ⁇ 2Si02/2)x(R ⁇ Si03/2)y(Si04/2) z , where R ⁇ and its proviso is defined above, and w, x, y, and z are independently from ⁇ 0 to ⁇ 1 , with the proviso that w+x+y+z 1 .
  • M, D, T, and Q units and their molar fractions influence subscript f in the average formula above.
  • T and Q units, indicated by subscripts y and z are typically present in silicone resins
  • D units, indicated by subscript x are typically present in silicone polymers (and may also be present in silicone resins).
  • Each R5 is independently selected, as introduced above, and may be linear, branched, cyclic, or combinations thereof.
  • Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups.
  • Aryl groups may be monocyclic or polycyclic.
  • Linear and branched hydrocarbyl groups may independently be saturated or unsaturated.
  • One example of a combination of a linear and cyclic hydrocarbyl group is an aralkyi group. Examples of substituted and unsubstituted hydrocarbyl groups are introduced above relative to R. Examples of aliphatically unsaturated group(s) are also introduced above.
  • the organopolysiloxane is substantially linear, alternatively is linear.
  • the substantially linear organopolysiloxane may have the average formula:
  • each R ⁇ and its proviso are defined above, and wherein f is selected such that 1 .9 ⁇ f ⁇ 2.2.
  • the substantially linear organopolysiloxane is typically a flowable liquid or is in the form of an uncured rubber.
  • the substantially linear organopolysiloxane has a viscosity of from 10 to 30,000,000 mPa-s, alternatively from 10 to 10,000 mPa-s, alternatively from 100 to 1 ,000,000 mPa-s, alternatively from 100 to 100,000 mPa-s, at 25 °C. Viscosity may be measured at 25 °C via a Brookfield LV DV-E viscometer, as understood in the art.
  • the organopolysiloxane may have the average formula: (R53Si0 1 /2) rT ( 5 2Si0 2 /2)n'(R 5 Si03/2)o,
  • each is independently selected and defined above (including the proviso that in each molecule, at least one is an aliphatically unsaturated group), and m' ⁇ 2, n' ⁇ 0, and o ⁇ 2.
  • m' is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6.
  • n' is from 0 to 1 ,000, alternatively from 1 to 500, alternatively from 1 to 200.
  • o is from 2 to 500, alternatively from 2 to 200, alternatively from 2 to 100.
  • the silicon-bonded aliphatically unsaturated group(s) may be pendent, terminal or in both pendent and terminal locations.
  • the organopolysiloxane may have the average formula:
  • any methyl group may be replaced with a vinyl or a substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenically unsaturated group, so long as at least two aliphatically unsaturated groups are present per molecule.
  • the organopolysiloxane may have the average formula:
  • n' and Vi are defined above.
  • the dimethyl polysiloxane terminated with silicon- bonded vinyl groups may be utilized alone or in combination with the dimethyl, methyl-vinyl polysiloxane disclosed immediately above.
  • any methyl group may be replaced with a vinyl or a substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenically unsaturated group, so long as at least two aliphatically unsaturated groups are present per molecule. Because the at least two silicon-bonded aliphatically unsaturated groups may be both pendent and terminal, the (A) organopolysiloxane may have the average formula:
  • the substantially linear organopolysiloxane can be exemplified by a dimethylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a methylphenylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylphenylsiloxane and dimethylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and a methylphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and diphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and di
  • the (A) organopolysiloxane may be a resinous organopolysiloxane.
  • the resinous organopolysiloxane may have the average formula:
  • the resinous organopolysiloxane has a branched or a three dimensional network molecular structure. At 25 °C, the resinous organopolysiloxane may be in a liquid or in a solid form, optionally dispersed in a carrier, which may solubilize and/or disperse the resinous organopolysiloxane therein.
  • the resinous organopolysiloxane may be exemplified by an organopolysiloxane that comprises only T units, an organopolysiloxane that comprises T units in combination with other siloxy units (e.g. M, D, and/or Q siloxy units), or an organopolysiloxane comprising Q units in combination with other siloxy units (i.e., M, D, and/or T siloxy units).
  • the resinous organopolysiloxane comprises T and/or Q units.
  • a specific example of the resinous organopolysiloxane is a vinyl-terminated silsesquioxane.
  • the organopolysiloxane may comprise a combination or mixture of different organopolysiloxanes, including those of different structures.
  • the (A) unsaturated compound may be a silicone-organic hybrid.
  • the (A) unsaturated compound may comprise the hydrosilylation reaction product of organopolysiloxanes (or of one or more organopolysiloxanes with one or more organic compounds), in which case the backbone of the (A) unsaturated compound may include organic divalent linking groups.
  • organohydrogensiloxanes may be reacted with other organopolysiloxanes, or with organic compounds, to give the (A) unsaturated compound.
  • the (A) unsaturated compound may be the reaction product of (a1 ) at least one Si-H compound and (b1 ) at least one compound having ethylenic unsaturation.
  • a molar excess of ethylenic unsaturated groups of the (b1 ) compound are utilized as compared to Si-H groups of the (a1 ) Si-H compound such that the (A) unsaturated compound includes at least one, alternatively an average of at least two, silicon-bonded aliphatically unsaturated groups.
  • the reaction product of the (a1 ) Si-H compound and the (b1 ) compound having ethylenic unsaturation may be referred to as an (AB)n type copolymer, with the (a1 ) Si-H compound forming units A and the (b1 ) compound having ethylenic unsaturation forming units B.
  • Combinations of different (a1 ) Si-H compounds may be utilized, and combinations of different (b1 ) compounds having ethylenic unsaturation may be utilized, such that the resulting (b) crosslinking agent comprises distinct units but may not be an (AB)n type copolymer.
  • the distinct units may be randomized or in block form.
  • the (A) unsaturated compound may comprise an organosilicon- compound, but not an organopolysiloxane.
  • the (A) unsaturated compound may comprise a silane, a disilane, or a siloxane (for example a disiloxane), while not constituting an organopolysiloxane.
  • a suitable silane is that of formula R 6 z "SiR 7 4_ z ", where each R 6 independently is an aliphatically unsaturated group, R 7 is independently a substituted or unsubstituted hydrocarbyl group, and 1 ⁇ z" ⁇ 4.
  • a siloxane is tetramethyldivinyldisiloxane.
  • the (A) unsaturated compound can be a single unsaturated compound or a combination comprising two or more different silicon hydride compounds.
  • composition and (A) unsaturated compound are subject to at least one of the following two provisos: (1 ) the (A) unsaturated compound also includes at least one silicon- bonded hydrogen atom per molecule; and/or (2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • the proviso (1 ) is true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule.
  • the proviso (2) is true such that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • both proviso (1 ) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • the proviso (1 ) is true and the (A) unsaturated compound includes at least one silicon-bonded hydrogen atom per molecule in addition to the aliphatically unsaturated group.
  • the (A) unsaturated compound may be any compound including at least one silicon-bonded hydrogen atom and at least one aliphatically unsaturated group.
  • the (A) unsaturated compound is typically an organosilicon compound and/or an organopolysiloxane.
  • organosilicon compounds including both aliphatic unsaturated and silicon-bonded hydrogen may be prepared from the unsaturated organic compounds disclosed above.
  • the organosilicon compound may also be a silane, disilane, siloxane, etc.
  • the organosilicon compound may be of formula
  • R6 b' H c'SiR 7 4-b'-c'' where R 6 and R 7 are independently selected and defined above, b' is 1 , 2, or 3, c' is 1 , 2, or 3, with the proviso that 2 ⁇ (b'+c') ⁇ 4.
  • the organopolysiloxane may have the formula R ⁇ 'He'SiO ⁇ .d'.e') ⁇ where R ⁇ is independently selected and defined above
  • the (A) unsaturated compound comprises the organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen
  • the silicon-bonded aliphatically unsaturated group(s) and the silicon-bonded hydrogen atom(s) may be present in any M, D, and/or T siloxy unit present in the organopolysiloxane, and may be bonded to the same silicon atom (in the case of M and/or D siloxy units).
  • the organopolysiloxane may comprise, for example, as M siloxy units: (R ⁇ SiO-i/ ⁇ ), (R5 2 HSiO-
  • the organopolysiloxane may comprise, for example, as D siloxy units: (R ⁇ SiC ⁇ ), (R5
  • the organopolysiloxane may comprise, for example, as T siloxy units: (R ⁇ SiC ⁇ ) and/or (HS1O3/2).
  • Such siloxy units may be combined in any manner, optionally along with Q siloxy units, to give an organopolysiloxane having at least one silicon-bonded aliphatically unsaturated group designated by R ⁇ and at least one silicon-bonded hydrogen atom.
  • the organopolysiloxane may have any one of the following formulas:
  • the proviso (2) is true and the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • the (B) silicon hydride compound may be any compound including at least one silicon-bonded hydrogen atom.
  • the (B) silicon hydride compound may be a silane compound, an organosilicon compound, an organohydrogensilane, an organohydrogensiloxane, etc.
  • the (B) silicon hydride compound can be linear, branched, cyclic, resinous, or have a combination of such structures.
  • the silicon- bonded hydrogen atom(s) can be located at terminal, pendant, or at both terminal and pendant positions.
  • Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms.
  • the (B) silicon hydride compound is of formula R ⁇ .gSiHg, where R8 is independently selected and may be any silicon-bonded group, and s is selected such that 1 ⁇ s ⁇ 4. Typically, s is 1 , 2, or 3, alternatively 1 or 2.
  • Each R ⁇ is typically independently a substituted or unsubstituted hydrocarbyl group.
  • the (B) silicon hydride is a silane compound
  • the (B) silicon hydride can be a monosilane, disilane, trisilane, or polysilane.
  • the (B) silicon hydride compound may be an organosilicon compound of formula: wherein each R9 IS an
  • g' is 0 or 1 .
  • R10 is a divalent linking group.
  • R " O may be a siloxane chain (including, for example, -
  • R ⁇ SiO-, -R ⁇ HSiO-, and/or -h ⁇ SiO- D siloxy units may be a divalent hydrocarbon group.
  • the divalent hydrocarbon group is free of aliphatic unsaturation.
  • the divalent hydrocarbon group may be linear, cyclic, branched, aromatic, etc., or may have combinations of such structures.
  • the (B) silicon hydride compound comprises an organohydrogensiloxane, which can be a disiloxane, trisiloxane, or polysiloxane.
  • organohydrogensiloxanes suitable for use as the (B) silicon hydride compound include, but are not limited to, siloxanes having the following formulae: PhSi(OSiMe2H)3,
  • organohydrogensiloxanes that are suitable for purposes of the (B) silicon hydride compound include 1 ,1 ,3,3-tetramethyldisiloxane, 1 ,1 ,3,3- tetraphenyldisiloxane, phenyltris(dimethylsiloxy)silane, 1 ,3,5-trimethylcyclotrisiloxane, a trimethylsiloxy-terminated poly(methylhydrogensiloxane), a trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), and a dimethylhydrogensiloxy-terminated poly(methylhydrogensiloxane).
  • the (B) silicon hydride compound comprises an organohydrogensiloxane
  • the (B) silicon hydride compound may comprise any combination of M, D, T and/or Q siloxy units, so long as the (B) silicon hydride compound includes at least one silicon-bonded hydrogen atom.
  • These siloxy units can be combined in various manners to form cyclic, linear, branched and/or resinous (three-dimensional networked) structures.
  • the (B) silicon hydride compound may be monomeric, polymeric, oligomeric, linear, branched, cyclic, and/or resinous depending on the selection of M, D, T, and/or Q units.
  • the (B) silicon hydride compound includes at least one silicon-bonded hydrogen atom
  • the (B) silicon hydride compound may comprise any of the following siloxy units including silicon-bonded hydrogen atoms, optionally in combination with siloxy units which do not include any silicon-bonded hydrogen atoms: (R 9 2 HSiO-
  • the (B) silicon hydride compound may have the average formula:
  • each R ⁇ is independently hydrogen or R 9 each R 9 is independently selected and defined above, and e" ⁇ 2, f"' ⁇ 0, and g" ⁇ 2.
  • e is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6.
  • f is from 0 to 1 ,000, alternatively from 1 to 500, alternatively from 1 to 200.
  • g is from 2 to 500, alternatively from 2 to 200, alternatively from 2 to 100.
  • the (B) silicon hydride compound is linear and includes one or more pendent silicon-bonded hydrogen atoms.
  • the (B) silicon hydride compound may be a dimethyl, methyl-hydrogen polysiloxane having the average formula;
  • the (B) silicon hydride compound is linear and includes terminal silicon-bonded hydrogen atoms.
  • the (B) silicon hydride compound may be an SiH terminal dimethyl polysiloxane having the average formula:
  • the SiH terminal dimethyl polysiloxane may be utilized alone or in combination with the dimethyl, methyl-hydrogen polysiloxane disclosed immediately above. Further, the SiH terminal dimethyl polysiloxane may have one trimethylsiloxy terminal such that the SiH terminal dimethyl polysiloxane may have only one silicon- bonded hydrogen atom. Alternatively still, the (B) organohydrogensiloxane may include both pendent and terminal silicon-bonded hydrogen atoms.
  • the (B) silicon hydride compound may have one of the following average formulas:
  • Some of the average formulas above for the (B) silicon hydride compound are resinous when the (B) silicon hydride compound includes T siloxy units (indicated by subscript h) and/or Q siloxy units (indicated by subscript i).
  • the (B) silicon hydride compound is typically a copolymer including T siloxy units and/or Q siloxy units, in combination with M siloxy units and/or D siloxy units.
  • the organohydrogenpolysiloxane resin can be a DT resin, an MT resin, an MDT resin, a DTQ resin, an MTQ resin, an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin, or an MDQ resin.
  • the (B) silicon hydride compound is resinous, or comprises an organopolysiloxane resin
  • the (B) silicon hydride compound typically has the formula:
  • the (B) silicon hydride compound may comprise an alkylhydrogen cyclosiloxane or an alkylhydrogen dialkyl cyclosiloxane copolymer, represented in general by the formula (R 1 2 2SiO) r i (R 1 2 HSiO) s i , where R 1 2 is independently selected and defined above, and where r' is an integer from 0-7 and s' is an integer from 3-10.
  • organohydrogensiloxanes of this type include (OSiMeH) 4 , (OSiMeH) 3 (OSiMeC 6 H 1 3 ), (OSiMeH) 2 (OSiMeC 6 H 1 3 )2, and
  • the (B) silicon hydride compound can be a single silicon hydride compound or a combination comprising two or more different silicon hydride compounds.
  • both proviso (1 ) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • suitable unsaturated compounds and silicon hydride compounds for this third embodiment are set forth above.
  • the (A) unsaturated compound, as well as the (B) silicon hydride compound, if present in the composition, may be disposed in a carrier vehicle. Examples of carrier vehicles are described.
  • the composition may comprise the (A) unsaturated compound and the (B) silicon hydride compound, when present, in varying amounts or ratios contingent on desired properties or end use application of the composition.
  • the composition comprises components (A) and (B) in an amount to provide a mole ratio of silicon-bonded hydrogen atoms to aliphatically unsaturated groups of from 0.3 to 5, alternatively from 0.6 to 3.
  • the composition further comprises (C) a catalyst.
  • the catalyst is set forth above. Depending on a selection of the components of the composition, the catalyst may serve as a hydrosilylation-reaction catalyst and/or a dehydrogenative silylation-reaction catalyst, as described below.
  • composition may further comprise one or more supplemental catalysts in combination with the (C) catalyst.
  • the supplemental catalyst typically comprises a Group 8 to Group 1 1 transition metal.
  • Group 8 to Group 1 1 transition metals refer to the modern lUPAC nomenclature.
  • Group 8 transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs);
  • Group 9 transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir);
  • Group 10 transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and
  • Group 1 1 transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations thereof, complexes thereof (e.g. organometallic complexes), and other forms of such metals may be utilized as the supplemental catalyst.
  • Additional examples of catalysts suitable for the supplemental catalyst include rhenium (Re), molybdenum (Mo), Group 4 transition metals (i.e., titanium (Ti), zirconium (Zr), and/or hafnium (Hf)), lanthanides, actinides, and Group 1 and 2 metal complexes (e.g. those comprising calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g. organometallic complexes), and other forms of such metals may be utilized as the supplemental catalyst.
  • Re rhenium
  • Mo molybdenum
  • Group 4 transition metals i.e., titanium (Ti), zirconium (Zr), and/or hafnium (Hf)
  • lanthanides actinides
  • Group 1 and 2 metal complexes e.g. those comprising calcium (Ca), potassium (K), strontium (Sr), etc.
  • the supplemental catalyst may be in any suitable form.
  • the supplemental catalyst may be a solid, examples of which include platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, and also nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, and also platinum-palladium, nickel-copper-chromium, nickel-copper- zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts comprising combinations of a plurality of metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts, and the like.
  • the supplemental catalyst comprises platinum.
  • the supplemental catalyst is exemplified by, for example, platinum black, compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, a reaction product of chloroplatinic acid and a monohydric alcohol, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated in a matrix or core-shell type compounds.
  • Microencapsulated hydrosilylation catalysts and methods of their preparation are also known in the art, as exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654, which are incorporated by reference herein in their entireties.
  • Complexes of platinum with organopolysiloxanes suitable for use as the supplemental catalyst include 1 ,3-diethenyl-1 ,1 ,3,3-tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix.
  • the supplemental catalyst may comprise 1 ,3-diethenyl-1 ,1 ,3,3-tetramethyldisiloxane complex with platinum.
  • the supplemental catalyst may be prepared by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or alkene-platinum-silyl complexes.
  • Alkene-platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (COD)PtCl2 with 0.045 mole COD and 0.0612 moles HMeSiC ⁇ .
  • the supplemental catalyst may also, or alternatively, be a photoactivatable hydrosilylation catalyst, which may initiate curing via irradiation and/or heat.
  • the photoactivatable hydrosilylation catalyst can be any hydrosilylation catalyst capable of catalyzing the hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of from 150 to 800 nanometers (nm).
  • the composition includes the (C) catalyst, but not the supplemental catalyst.
  • the (C) catalyst is present in the composition in a catalytic amount, i.e., an amount or quantity sufficient to promote a reaction or curing thereof at desired conditions.
  • the catalytic amount of the (C) catalyst may be greater than 0.01 ppm, and may be greater than 1 ,000 ppm (e.g., up to 10,000 ppm or more).
  • the typical catalytic amount of (C) catalyst is less than 5,000 ppm, alternatively less than 2,000 ppm, alternatively less than 1 ,000 ppm (but in any case greater than 0 ppm).
  • the catalytic amount of the (C) catalyst may range from 0.01 to 1 ,000 ppm, alternatively 0.01 to 100 ppm, and alternatively 0.01 to 50 ppm of metal based on the weight of the composition.
  • the ranges may relate solely to the metal content within the (C) catalyst or to the (C) catalyst altogether (including its ligands). In certain embodiments, these ranges relate solely to the metal content within the (C) catalyst.
  • the composition may further comprise one or more optional components, including adhesion promoters, carrier vehicles, dyes, pigments, anti-oxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (including extending and reinforcing fillers), surfactants, thixotroping agents, water, carrier vehicles or solvents, pH buffers, etc.
  • the composition may be in any form and may be incorporated into further compositions, e.g. as a component of a composition.
  • the composition may be in the form of, or incorporated into, an emulsion.
  • the emulsion may be an oil-in-water emulsion, water-in- oil emulsion, silicone-in-oil emulsion, etc.
  • the composition itself may be a continuous or discontinuous phase of such an emulsion.
  • Suitable carrier vehicles include silicones, both linear and cyclic, organic oils, organic solvents and mixtures of these. Specific examples of solvents may be found in U.S. Pat. No. 6,200,581 , which is hereby incorporated by reference for this purpose. Examples of suitable organic carrier vehicles are set forth above with respect to the catalyst.
  • the carrier vehicle may also be a low viscosity organopolysiloxane or a volatile methyl siloxane or a volatile ethyl siloxane or a volatile methyl ethyl siloxane having a viscosity at 25° C in the range of 1 to 1 ,000 mm 2 /sec, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, ecamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, exadeamethylheptasiloxane, heptamethyl-3- ⁇ (trimethylsilyl)oxy) ⁇ trisiloxane, hexamethyl-3,3, bis ⁇ (
  • composition may be prepared by combining components (A)-(C), along with any optional components, in any order of addition, optionally with a master batch, and optionally under shear.
  • a method of preparing a hydrosilylation reaction product is also provided.
  • the hydrosilylation reaction product is formed from the composition and may take a variety of forms depending on a section of the components in the composition.
  • the method comprises reacting an aliphatically unsaturated group and a silicon- bonded hydrogen atom in the presence of (C) a hydrosilylation catalyst to give the hydrosilylation reaction product.
  • the (C) hydrosilylation catalyst is the (C) catalyst described above.
  • the hydrosilylation reaction product is formed by an addition reaction between the silicon-bonded hydrogen atom and the aliphatically unsaturated group.
  • the (C) hydrosilylation catalyst and inventive method can be utilized in any hydrosilylation reaction, e.g. in lieu of or in addition to conventional hydrosilylation catalysts.
  • the (C) hydrosilylation catalyst is generally less expensive than conventional hydrosilylation catalysts based on platinum, while still having excellent catalytic activity.
  • the aliphatically unsaturated group is present in the (A) unsaturated compound.
  • At least one of the following two provisos applies: (1 ) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the silicon- bonded hydrogen atom is present in the (B) silicon hydride compound separate from the (A) unsaturated compound.
  • the proviso (1 ) is true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule.
  • the proviso (2) is true such that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • both proviso (1 ) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and that the composition further comprises the (B) silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • the aliphatically unsaturated group and the silicon-bonded hydrogen atom react in the presence of the (C) hydrosilylation reaction catalyst.
  • the (A) unsaturated compound and/or the (B) silicon hydride compound, and/or a moiety thereof, may interact with the (C) hydrosilylation catalyst, and thus become X or L as defined above.
  • the (A) unsaturated compound and/or the (B) silicon hydride compound may interact with the (C) hydrosilylation catalyst by displacing X or L, and thus become X or L as defined above via substitution.
  • the hydrosilylation-reaction product prepared via the method is not limited and is generally a function of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound.
  • the hydrosilylation-reaction product may be monomeric, oligomeric, polymeric, resinous, etc.
  • the hydrosilylation-reaction product may comprise a fluid, an oil, a gel, an elastomer, a rubber, a resin, etc.
  • the hydrosilylation-reaction product may take any form, as understood in the art, based on the selection of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound.
  • the method utilizes 1 -octene as the (A) unsaturated compound and two different (B) silicon hydride compounds.
  • the catalyst is the (C) hydrosilylation catalyst.
  • the method may be utilized to prepare hydrosilylation-reaction products in the form of functionalized, e.g. olefin functionalization, silanes or siloxanes.
  • functionalized silanes or siloxanes may be utilized in other end use applications, e.g. as a discrete component in another composition, including a curable composition, a personal care or cosmetic composition, etc.
  • the hydrosilylation-reaction product may also include various byproducts formed via the hydrosilylation reaction.
  • the hydrosilylation-reaction product typically includes a target species and various byproducts.
  • the hydrosilylation-reaction product may also include other components, e.g. a carrier or solvent, if the method and reaction is carried out therein and/or if the composition includes such components.
  • the method may further comprise isolating the target species, e.g. via any suitable purification method.
  • a method of preparing a dehydrogenative silylation reaction product is also provided.
  • the dehydrogenative silylation reaction product is formed from the composition and may take a variety of forms depending on a section of the components in the composition.
  • the method comprises reacting an aliphatically unsaturated group and a silicon- bonded hydrogen atom in the presence of (C") a silylation catalyst to give the dehydrogenative silylation reaction product.
  • the (C") silylation catalyst is the (C) catalyst described above.
  • the dehydrogenative silylation reaction product is formed by a dehydrogenative silylation reaction between the silicon-bonded hydrogen atom and the aliphatically unsaturated group.
  • Hydrogen gas (H2) is generally a byproduct of the dehydrogenative silylation reaction.
  • the liberation of hydrogen gas (H2) may result in a further side reaction between the hydrogen gas (H2) and the aliphatically unsaturated group, which may hydrogenate the aliphatically unsaturated group in situ.
  • dehydrogenative silylation does not involve saturation of the aliphatically unsaturated group.
  • dehydrogenative silylation reactions are particularly desirable for functionalization of silanes or siloxanes, e.g. to impart ethylenic unsaturation.
  • the (C") silylation catalyst and inventive method can be utilized in any dehydrogenative silylation reaction, e.g. in lieu of or in addition to conventional silylation catalysts.
  • the (C") silylation catalyst is generally less expensive than conventional silylation catalysts based on platinum, while still having excellent catalytic activity.
  • the aliphatically unsaturated group is present in the (A) unsaturated compound.
  • At least one of the following two provisos applies: (1 ) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the silicon- bonded hydrogen atom is present in the (B) silicon hydride compound separate from the (A) unsaturated compound.
  • the proviso (1 ) is true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule.
  • the proviso (2) is true such that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • both proviso (1 ) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and that the composition further comprises the (B) silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.
  • the dehydrogenative silylation reaction product prepared via the method is not limited and is generally a function of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound.
  • the dehydrogenative silylation reaction product may be monomeric (e.g. a silane), oligomeric, polymeric, resinous, etc.
  • the dehydrogenative silylation reaction product may comprise a fluid, an oil, a gel, an elastomer, a rubber, a resin, etc.
  • the hydrosilylation-reaction product may take any form, as understood in the art, based on the selection of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound.
  • the dehydrogenative silylation reaction product includes at least one aliphatically unsaturated group per molecule, attributable to the (A) unsaturated compound.
  • the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound may be selected based on a desired target species of the hydrosilylation-reaction product.
  • the (B) silicon hydride may be a polymer or resin such that the method may be utilized to impart ethylenic unsaturation to such polymer or resin.
  • the dehydrogenative silylation reaction product comprises an alkenyl-functional compound. This is typically the case when the (B) silicon hydride compound is utilized separate from the (A) unsaturated compound.
  • the alkenyl group of the alkenyl-functional compound is formed from the unsaturated compound, which bonds to silicon via dehydrogenative silylation in the dehydrogenative silylation reaction product.
  • the method may be utilized to prepare dehydrogenative silylation products in the form of functionalized, e.g. olefin functionalization, silanes or siloxanes.
  • functionalized silanes or siloxanes may be utilized in other end use applications, e.g. as a discrete component in another composition, including a curable composition, a personal care or cosmetic composition, etc.
  • the dehydrogenative silylation reaction product includes at least one aliphatically unsaturated group per molecule
  • the dehydrogenative silylation reaction product may be utilized in further reactions, e.g. in a hydrosilylation reaction.
  • the dehydrogenative silylation reaction product may be a component in a hydrosilylation-curable composition.
  • the dehydrogenative silylation reaction product may also include various byproducts formed via the dehydrogenative silylation reaction.
  • the dehydrogenative silylation reaction product typically includes a target species and various byproducts.
  • the dehydrogenative silylation reaction product may also include other components, e.g. a carrier or solvent, if the method and reaction is carried out therein and/or if the composition includes such components.
  • the method may further comprise isolating the target species, e.g. via any suitable purification method.
  • ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range of “at least 10” inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.
  • each R is an isopropyl group.
  • Ligand 2 has the following structure:
  • each R is a tetrafluorophenyl group.
  • the Complex 1 has the following structure:
  • the Complex 2 has the following structure:
  • the Complex 3 has the following structure:
  • the Complex 4 has the following structure:
  • the Complex 5 has the following structure:
  • Examples 1 -7 an (A) unsaturated compound is reacted with a (B) silicon hydride compound in the presence of a (C") silylation catalyst to give a dehydrogenative silylation reaction product.
  • the (C") silylation catalyst corresponds to certain complexes made in Preparation Examples 1 -5 relating to Complexes 1 -5, but in their activated form from being reacted in situ with an activating agent.
  • the (A) unsaturated compound comprises ethylene.
  • Silicon hydride compound 1 is triphenylsilane.
  • Silicon hydride compound 2 is triethoxysilane.
  • Silicon hydride compound 3 is heptamethyltrisiloxane.
  • Activated complex 1 is Complex 1 as prepared above reacted in situ with 2.2 equivalents of NaBEt3H as an activating agent.
  • Activated complex 5 is Complex 5 as prepared above reacted in situ with 2.2 equivalents of NaBEt3H as an activating agent.
  • Activated complex 3 is Complex 3 as prepared above reacted in situ with 2.2 equivalents of NaBEt3H as an activating agent.
  • each (C") silylation catalyst is utilized in an amount of 2 mol% (based on the overall (C" silylation catalyst, and not just the metal therein).
  • Each (B) silicon hydride compound is utilized in an amount of 0.5 mmol.
  • Each reaction is carried out in a 85 mL Fischer-Porter reactor saturated with 2 atm ethylene and in 2 mL toluene as a vehicle. More specifically, after loading the reactor with the (B) silicon hydride compound, toluene, and (C") silylation catalyst, the contents of the reactor are frozen and the headspace is evacuated. The headspace of the reactor is then filled with 2 atm of ethylene, and the reactor is heated at 70 °C at constant pressure of ethylene. After 2 hours, the contents of the reactor are exposed to air to quench the reaction, filtered through a plug of silica gel, and purified by removing volatiles under vacuum.
  • Examples 8-12 an (A) unsaturated compound is reacted with a (B) silicon hydride compound in the presence of a (C) catalyst to give a reaction product.
  • the catalyst may be considered a (C) hydrosilylation catalyst and/or a (C") silylation catalyst based on the reaction product form.
  • the (C) catalyst corresponds to certain complexes made in Preparation Examples 1 -5 relating to Complexes 1 -5.
  • Table 2 below sets forth the particular (A) unsaturated compound, (B) silicon hydride and (C) catalyst utilized in each of Examples 8-12.
  • the (A) unsaturated compound has the following structure:
  • the (B) silicon hydride compound has the following structure:
  • Example 8 is carried out at 25 °C;
  • Example 9 is carried out at 65 °C;
  • Example 10 is carried out from - 30 to 25 °C;
  • Example 1 1 is carried out at 65 °C; and
  • Example 12 is carried out at 65 °C.
  • each (C) catalyst is utilized in an amount of 1 mol% (based on the overall (C" silylation catalyst, and not just the metal therein). In Examples 10-12, each (C) catalyst is utilized in an amount of 0.5 mol%

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Abstract

L'invention concerne un catalyseur ayant une structure spécifique et un procédé d'élevage du catalyseur. L'invention concerne également une composition qui comprend : (A) un composé insaturé comprenant au moins un groupe aliphatique insaturé par molécule, soumis à au moins l'une des deux conditions suivantes : (1) le composé insaturé (A) comprenant également au moins un atome d'hydrogène lié au silicium par molécule ; et/ou (2) la composition comprend également (B) un composé d'hydrure de silicium comprenant au moins un atome d'hydrogène lié au silicium par molécule. La composition comprend en outre (C) le catalyseur. L'invention concerne également un procédé de préparation d'un produit de réaction d'hydrosilylation et un produit de réaction de silylation déshydrogénante.
PCT/US2018/042421 2017-07-17 2018-07-17 Catalyseur et procédés associés impliquant une hydrosilylation et une silylation déshydrogénante WO2019018357A1 (fr)

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US16/632,150 US10946368B2 (en) 2017-07-17 2018-07-17 Catalyst and related methods involving hydrosilylation and dehydrogenative silylation
CN201880044594.2A CN110944748B (zh) 2017-07-17 2018-07-17 涉及氢化硅烷化和脱氢硅烷化的催化剂和相关方法
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